U.S. patent number 4,007,228 [Application Number 05/069,116] was granted by the patent office on 1977-02-08 for substituted-2-nitro-paraphenylenediamines and processes for producing same.
This patent grant is currently assigned to L'Oreal. Invention is credited to Andree Bugaut, Gregoire Kalopissis.
United States Patent |
4,007,228 |
Kalopissis , et al. |
February 8, 1977 |
Substituted-2-nitro-paraphenylenediamines and processes for
producing same
Abstract
The compound
(2'-hydroxyethyl)-1-amino-2-nitro-(2'-hydroxyethyl)-4-methylamino
benzene which can be used to dye live human hair.
Inventors: |
Kalopissis; Gregoire (Paris,
FR), Bugaut; Andree (Boulogne-sur-Seine,
FR) |
Assignee: |
L'Oreal (Paris,
FR)
|
Family
ID: |
27350592 |
Appl.
No.: |
05/069,116 |
Filed: |
September 2, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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508568 |
Nov 18, 1965 |
3555584 |
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Foreign Application Priority Data
Current U.S.
Class: |
564/400; 564/424;
564/441; 564/393 |
Current CPC
Class: |
A61K
8/418 (20130101); A61Q 5/065 (20130101) |
Current International
Class: |
C07C 091/06 () |
Field of
Search: |
;260/573 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1,137,922 |
|
Jan 1957 |
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FR |
|
13,956 |
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Apr 1905 |
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UK |
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Other References
Vogel, Arthur I., Practical Organic Chemistry, Third Edition, pp.
122-133, John Wiley & Sons, Inc. New York, New York..
|
Primary Examiner: Warren; Charles F.
Attorney, Agent or Firm: Brisebois & Kruger
Parent Case Text
SUMMARY OF THE INVENTION
This application is a division of application Ser. No. 508,568,
filed Nov. 18, 1965 which is now U.S. Pat. No. 3,555,584.
Claims
What is claimed is:
1.
(2'-hydroxyethyl)-1-amino-2-nitro-(2'-hydroxyethyl)-4-methylamino
benzene.
2. The method of making a high purity
(2'-hydroxy-ethyl)-1-amino-2-nitro-(2'-hydroxyethyl)-4-methylamino
benzene of claim 1 which comprises the steps of reacting
1-amino-2-nitro-4-methyl-acetamino benzene with reactive amounts of
chloroethylchloro-formiate to obtain the chloroethylic ester of
(-2-nitro-4-methylacetamino) phenylcarbamic acid, deacetylizing the
resulting product with deacetylating amounts of concentrated
hydrochloric acid to obtain the chloroethylic ester of
(2-nitro-4-methylamino)-phenylcarbamic acid, reacting this product
with a potash solution to obtain
(2'-hydroxyethyl)-1-amino-2-nitro-4-methylamino benzene, and then
reacting this product with glycol halohydrine to produce
(2'hydroxyethyl)-1-amino-2-nitro-(2'hydroxyethyl)-4-methylamino
benzene.
3. The method of claim 2 in which said halohydrine is bromohydrine.
Description
Substituted nitroparaphenylenediamines are well known active
ingredients of hair dyes, and particularly of dyes for human hair.
Among the different substituents proposed with a view to obtaining
deeper shades than those obtained with nitroparaphenylenediamine
itself are the alkyl groups and the hydroxyalkyl groups. In
particular it has been suggested that the trihydroxyalkylated
derivatives of nitroparaphenylenediamine be used, and especially
those trihydroxyethylated derivatives which have a hydroxyethyl
radical on the amino group in the ortho position of the nitro group
and two hydroxyethyl radicals on the amino group in the meta
position of the nitro group.
However, it is very difficult to obtain a trihydroxyethylated
derivative of the type in question from nitroparaphenylenediamine,
by reaction with a halohydrine, for example, in a commerically
adequate percentage of yield, without painstaking purification,
because the substitution of the hydroxyethylated groups for the
hydrogens of the amine functions leads in practice, not to a pure
trihydroxyethylated product, but to a mixture of mono-, di-, and
trisubstituted products, each having its own coloring power, said
mixture often comprising also tarray impurities.
Under the operating conditions under which this substitution is
carried out, the proportions in such a mixture vary, and the
results obtained by using such a mixture cannot be consistently
reproduced.
The object of the present invention is to provide a new dye and new
coloring compositions based on said new dye.
The said new dye is:
(2'-hydroxyethyl)- 1-amino- 2-nitro-( 2' -hydroxyethyl)- 4
-methylamino benzene.
The invention also relates to two processes of preparing this new
dye.
The first method described below in Example A results in a mixture
comprising a mixture of the product of this invention which is
di-hydroxyethylated in 1-4 position and a product which is
mono-hydroxyethylated in position 4, while the amine function which
occupies position 1 in the dye according to the invention remains
unsubstituted. The process of separating the reaction products
obtained by this process is long and difficult, but it is highly
important that this separation be made, because the presence of the
mono-hydroxyethylated product has a substantial effect on the shade
produced and if a mixture of both these reaction products is used,
the fact that the proportion between the products is dependent on
the reaction conditions makes it impossible to obtain a perfectly
reproducible shade. The use of this first method of preparation is
therefore accompanied by definite inconveniences. This process has,
however, been described, since the dye according to the invention
may be produced in this manner. Said process is essentially
characterized by the fact that a glycol halohydrine is reacted with
1-amino-2-nitro-4-methylamino benzene, (a composition heretofore
known in itself) and that the resulting mono and
di-hydroxyethylated products are then separated.
The second process of preparing the dye according to the invention,
which is described in Example B, makes it possible to efficiently
substitute a hydroxyethyl radical for a hydrogen of the amine
function in the ortho position of the nitro group. This process is
essentially characterized by the fact that
1-amino-2-nitro-4-methylacetamino-benzene is reacted with
chloroethyl-chloroformiate to block the position occupied by one of
the hydrogen atoms initially bonded to the nitrogen atom in
position 1 and the fact that concentrated hydrochloric acid is used
to deacetylate the product thereby obtained, after which potash is
added to cause hydroxyethylation in position 1 and a glycol
halohydrine is introduced to cause hydroxyethylation in position
4.
It has been found that the use of (2' -hydroxyethyl)-
1-amino-2-nitro-(2' -hydroxyethyl- 4-methylamino-benzene produces
perfectly uniform deep violet shades on live human hair.
Moreover, this dye has an excellent affinity for the keratinic
fibers of human hair and the colors produced thereby are
particularly resistant to shampooing and have no coloring effect on
the scalp.
The hair dyeing compositions containing this dye are simple aqueous
solutions having preferably an alkaline pH. The pH of these
solutions is generally between 7 and 10 and preferably between 8
and 9.5. Ammonia, or any organic base such as an alkylamine, an
alkanolamine, or a heterocyclic amine may be used to adjust the
pH.
Moreover, the dyeing solutions according to the invention may
include various conventional ingredients such as, for example,
organic solvents, detergents, and lacquers, that are suitable for
use on live human hair.
The dye of this invention may also be mixed with other dyes such as
nitrated dyes, azo dyes, anthroquinone dyes, or any other type of
dye conventionally used to dye human hair to produce a variety of
different hair colors.
In use, these dyes do not require the employment of an oxidizing
agent. The time in contact with the hair may vary within broad
limits but falls preferably between 5 and 30 minutes. The
temperature of application may also be varied, but the dye is
preferably used at room temperature. The concentration of the dye
of this invention in the dyeing solutions may also be varied, but
this concentration is preferably between 0.1 and 3%.
The processes of preparing the dye of this invention will now be
described in Examples A and B. It will be recalled that the process
of Example A is more difficult to carry out than the process of
Example B.
EXAMPLE A
First process of preparing
(2'-hydroxyethyl)-1-amino-2-nitro-(2'-hydroxyethyl)-4-methylamino
benzene.
A mixture containing 0.05 mols (8.35 g) of
1-amino-2-nitro-4-methylamino benzene, 65 cm.sup.3 of water and 9.6
g of calcium carbonate is heated to reflux. 0.2 mols (14 cm.sup.3)
of glycol bromohydrine is added little by little and kept at reflux
for an hour and a half. After cooling the mixture is acidified,
using 12 cm.sup.3 of hydrochloric acid to destroy the excess
calcium carbonate, and brought to an alkaline pH, using ammonia.
Since it is difficult to substitute a hydrogen of the amine
function in the ortho position of the nitro group, this process
always yields a mixture of the product sought and
1-amino-2-nitro-(2'-hydroxyethyl)-4-methylamino benzene.
These two products are separated in the following manner: The
resulting mixture is drained to yield 4.5 g of a product which
melts at 110.degree. C and consists almost entirely of the
monohydroxyethylated derivative. After several recrystallizations,
3 g of pure 1-amino-2-nitro-(2'-hydroxyethyl)-4-methylamino
benzene, which melts at 114.degree. C, is obtained. The isomer
(2'-hydroxyethyl)-1-amino-2-nitro-4-methylamino benzene melts at
120.degree. C and the mixture of these two isomers melts at
100.degree. C.
______________________________________ Calculated Found
______________________________________ C % 51.18 50.89 - 50.98 H %
6.16 6.16 - 6.43 N % 19.90 20.21 - 20.23
______________________________________
This mono-hydroxyethylated product may also be used as a hair
dye.
In order to obtain the di-hydroxyethylated product after the above
draining step, the mother liquid is extracted, using
methyl-isobutyl-ketone and vacuum concentrated. After cooling, the
yield is 3.8 g of a raw product which melts at 80.degree. C and the
major part of which consists of the dihydroxyethylated derivative.
After recrystallization in ethyl acetate, 2.7 g of
(2'-hydroxyethyl)-amino-2-nitro-(2'-hydroxyethyl)-4-methylamino
benzene which melts at 99.degree. C is obtained by drying.
EXAMPLE B
Second method of preparing
(2'-hydroxyethyl)-1-amino-2-nitro-(2'-hydroxyethyl)-4-methylamino
benzene.
This process is carried out in four steps:
a. Preparation of the .beta. -chloroethylic ester of
(2-nitro-4-methylacetamino) phenylcarbamic acid.
0.17 mols (35 g) of 1-amino-2 -nitro-4-methylacetamino benzene are
dissolved in 200 cm.sup.3 of methyl-isobutyl-ketone. After adding
12 g of calcium carbonate 0.2 mols (28.8 g) of
chlorethyl-chloroformiate is introduced little by little, at reflux
and while stirring. Reflux is maintained for three hours. The
product is filtered while boiling to eliminate mineral salts. The
solvent is driven off under vacuum and the oily residue is treated
with ether to crystallize it. Drying yields 44 g of the .beta.
chloroethylic ester of (2-nitro-4-methyl-acetamino-phenylcarbamic
acid, which melts at 83.degree. C.
______________________________________ Calculated Found
______________________________________ C % 45.64 45.46 - 45.55 H %
4.43 4.62 - 4.50 N % 13.31 13.16 - 13.32
______________________________________
b. Preparation of the .beta. chloroethylic ester of
(2-nitro-4-methylamino)-phenylcarbamic acid.
0.232 mols (73.3 g) of the .beta. chloroethylic ester of
(2-nitro-4-methylacetamino) phenylcarbamic acid are introduced into
a mixture containing 79 cm.sup.3 of concentrated hydrochloric acid,
158 cm.sup.3 of water and 43 cm.sup.3 of acetic acid. This is
brought to reflux for an hour, cooled in a mixture of ice and salt
and yields 58 g of crystallized hydrochlorate on drying. The
hydrochlorate is dissolved in water, brought to an alkyline pH with
ammonia, and 49 g of the .beta. chloroethylic ester of
(2-nitro-4-methylamino)-phenylcarbamic acid is obtained on drying.
This ester melts at 90.degree. C.
______________________________________ Calculated Found
______________________________________ C % 43.87 44.13 - 44.01 H %
4.38 4.56 - 4.48 N % 15.35 15.63 - 15.05
______________________________________
c. Preparation of (2'-hydroxyethyl)-1-amino-2-nitro-4-methylamino
benzene.
0.056 mols (15.5 g) of the .beta. chloroethylic ester of
(2-nitro-4-methylamino)-phenylcarbamic acid is heated to reflux for
two hours in 140 cm.sup.3 of an alcoholic potash solution
containing 110 g of potash per liter. This is cooled, emptied into
a liter of ice water and dried to yield 9.5 g of
(2'-hydroxyethyl)-1-amino-2-nitro-4-methylamino benzene which melts
at 120.degree. C.
______________________________________ Calculated Found
______________________________________ C% 51.18 51.39 - 51.31 H%
6.16 6.39 - 6.30 N% 22.74 22.54 - 22.62
______________________________________
d. Preparation of
(2'-hydroxyethyl)-1-amino-2-nitro-(2'-hydroxyethyl)-4-methylamino
benzene.
The substitution of a hydrogen of the amine function in the meta
position of the nitro group is easily accomplished in the following
manner. A mixture of 0.086 mols (18.1 g) of
(2'-hydroxyethyl)-1-amino-2-nitro-4-methylamino benzene with 110
cm.sup.3 of water and 6.25 g of calcium carbonate is brought to
reflux. 0.124 mols (8.75 cm.sup.3) of glycol bromohydrine is then
introduced drop by drop, while stirring. Reflux is maintained for
an hour and a half and then the reaction mixture is cooled and
acidified with hydrochloric acid. The crystallized hydrochlorate is
then dried, redissolved in water, and brought to an alkaline pH by
adding ammonia. Drying yields 16 g of
(2'-hyroxyethyl)-1-amino-2-nitro-(2'-hydroxyethyl)-4-methylamino
benzene which melts at 99.degree. C.
______________________________________ Calculated Found
______________________________________ C% 51.76 51.64 - 51.90 H%
6.66 6.83 - 6.85 N% 16.47 16.34 - 16.57
______________________________________
Several examples showing how the dye according to the invention may
be used to color the hair will now be given.
EXAMPLE 1
The following solution is prepared:
______________________________________
(2'-hydroxyethyl)-1-amino-2-nitro-(2'-hydroxyethyl)- 4-methylamino
benzene 0.5 g. Lauric alcohol oxyethylenated with 20 molecules of
ethylene oxide 5 g. Ammonia q.s.p. pH 9 Water q.s.p. 100
______________________________________
This solution is applied to completely white hair and left for ten
minutes. The hair is then rinsed, washed, and dried, and the shade
obtained is mauve.
EXAMPLE 2
The following solution is prepared:
______________________________________
(2'-hydroxyethyl)-1-amino-2-nitro- (2'-hydroxyethyl)-4-methylamino
benzene 0.7 g. 1-hydroxy-2-amino-5-nitro-benzene 0.12 g. Sodium
salt of N-(N',N'-diethylaminopropyl)- N.sup.2 -fatty
alkyl-asparagine having the formula: ##STR1## in which R is the
alkyl residue of the fatty acids of copra 1 g. 50% solution of
sodium salt of N(N',N'- diethylaminopropyl)-N.sub.2 -fatty
alkyl-asparagine having the formula: ##STR2## in which R represents
the alkyl residue of the fatty acids of tallow 1 g. Lauric alcohol
oxyethylenated with 20 molecules of ethylene oxide 3 g.
Diethanolamide of copra 2 g. Ammonia q.s.p. pH 9 Water q.s.p. 100
g. ______________________________________
This solution is applied to 90% white hair for 20 minutes. The hair
is then rinsed and washed. After drying, a clear chestnut is
obtained.
EXAMPLE 3
The following solution is prepared:
______________________________________
(2'-hydroxyethyl)-1-amino-2-nitro- (2'-hydroxyethyl)-4-methylamino
benzene 0.6 g. 1-hydroxy-2-amino-5-nitro benzene 0.1 g.
Nitroparaphenylenediamine 0.01 g. 1-amino-2-nitro-4-methylamino
benzene 0.07 g. Sodium salt of N(N',N'-diethylaminopropyl)- N.sup.2
-alkyl-asparagin having the formula: ##STR3## in which R is the
alkyl residue of the fatty acids of copra 1 g. 50% solution of the
sodium salt of N(N',N'- diethylaminopropyl)-N.sub.2
-alkyl-asparagine having the formula: ##STR4## in which R
represents the alkyl residue of the fatty acids of tallow 1 g.
Lauric alcohol oxyethylenated with 20 molecules of ethylene oxide 3
g. Diethanolamide of copra 2 g. Ammonia q.s.p. pH 9 Water q.s.p.
100 g. ______________________________________
This solution is applied to 90% white hair for 20 minutes. The hair
is then rinsed and washed. After drying, a reddish chestnut is
obtained.
* * * * *